CN101272856B - Carbonylation method by adding secondary sterically hindered amines - Google Patents

Carbonylation method by adding secondary sterically hindered amines Download PDF

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CN101272856B
CN101272856B CN200680032939XA CN200680032939A CN101272856B CN 101272856 B CN101272856 B CN 101272856B CN 200680032939X A CN200680032939X A CN 200680032939XA CN 200680032939 A CN200680032939 A CN 200680032939A CN 101272856 B CN101272856 B CN 101272856B
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CN101272856A (en
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D·赫斯
D·奥尔特曼
O·莫勒
K·-D·威斯
D·弗里达格
W·巴施肯
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Evonik Operations GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0237—Amines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
    • B01J31/0247—Imides, amides or imidates (R-C=NR(OR))
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation

Abstract

The invention relates to a method for converting carbonylatable compound by means of a metal complex catalyst comprising a sub-group VIII metal and an organophosphoric ligand in the presence of a secondary sterically hindered amine.

Description

By adding the carbonylation method that secondary sterically hindered amines carries out
But the present invention relates in the presence of the metal complex catalysts of forming by the metal and the phosphorus organic ligand of VIII subgroup and in the presence of secondary sterically hindered amines, be used for the carbonylation method of the reaction of carbonylated compounds.
Carbonylation method is the common method in the organic chemistry.Therefore, aldehyde can pass through the olefin production of catalysis hydroformylation (or oxo synthesis) from a few carbon atom.The hydrogenation of these aldehyde obtains alcohols, and this alcohol for example is used to prepare plasticizer or as washing agent.The oxidation of aldehyde obtains carboxylic acids, and the latter can for example be used to produce coating with dry promoter or as the stabilizing agent of PVC.
The process that obtains having the aldehydes of many carbon atoms in the reaction between olefin(e) compound, carbon monoxide and the hydrogen in the presence of the catalyst is known as hydroformylation (oxo synthesis).As the catalyst in these reactions, usually use the compound of transition metal of 8 to 10 families of the periodic table of elements, especially the compound of the compound of rhodium and cobalt.Use the hydroformylation of rhodium compound to compare the advantage that higher chemo-selective and better utilization rate of raw materials generally are provided with the catalysis of using cobalt compound, and usually be more economical therefore.The hydroformylation of rhodium catalysis utilizes complex to carry out usually, and this complex is by rhodium and preferably be made of as part trivalent phosphorous compound.Known part is the compound of phosphine, phosphite ester and phosphiinic acid ester for example.The formylated summary of hydrogenation of olefins sees B.CORNILS, W.A.HERRMANN, " Applied Homogeneous Catalysis withOrganometallic Compounds ", Vol.1﹠amp; 2, VCH, Weinheim, New York, 1996.
Each catalyst system (cobalt or rhodium) has its certain benefits.Use different catalyst systems according to initiation material and target product.If use rhodium and triphenylphosphine, alpha-olefin can be by hydroformylation under pressure and temperature lower when using Co catalysts.As phosphorous part, use excessive triphenylphosphine usually, high part/rhodium ratio is that the reaction selectivity of the industrial needed positive aldehyde product of raising generation is needed.
US-A-4,694,109 and US-A-4,879,416 relate to biphosphine ligand and their uses in the hydroformylation at alkene under the low synthesis gas pressure.Especially for the hydroformylation of propylene, can realize high activity and high just/different selectivity by the part that uses this type.
WO-A-95/30680 describes bidentate phosphine ligands and their uses in catalysis, the especially use in hydroformylation reaction.
Two phosphines of ferrocene bridging are at for example US-A-4, and 169,861, US A-4 is disclosed the part as hydroformylation in 201,714 and US-A-4,193,943.
The shortcoming of bidentate phosphine ligands is the preparation process of relative complex.Therefore in industrial process, use this system usually not have cost benefit.In addition, bi-ester of phosphite is unsettled relatively.Therefore, EP 0 676 405 bin stability of having put down in writing phosphite ester and phosphinate can improve by organic amine with in conjunction with the interpolation of slaine of acid.
Rhodium-single phosphite ester complex is the suitable catalyst of hydroformylation with branched olefin of internal double bond, but is low for the selectivity of terminal hydroformylation compound.EP-A-0 155508 discloses single phosphite ester that two arlydene replace in for example use in the rhodium catalytic hydroformylation of isobutene of steric hindrance alkene.
The complex-catalyzed hydroformylation with linear alpha-olefin of terminal and internal double bond of rhodium-bis-phosphite forms the product of main terminal hydroformylation, and usually reacts on than low degree near the branched olefin that has internal double bond the branch.In being coordinated in transition metal in the heart the time, these phosphite esters obtain having the catalyst of the activity of raising, but are not satisfied the service life of these catalyst systems, especially because the hydrolysis and the oxidation sensitive of phosphite ester ligand.Important improvement can realize as the initiation material of phosphite ester ligand by the two aryl-diols that use to replace, as described in EP-A-0 214 622 or the EP-A-0 472 071.
According to the document, the rhodium complex in these parts is the extremely active hydroformylation catalysts of alpha-olefin.US-A-4,668,651, US-A-4,748,261 and US-A-4,885,401 describe poly-phosphite ester ligand, utilize it to make alpha-olefin and 2-butylene can be converted to the product of terminal hydroformylation with high selectivity.At US-A-5, in 312,996, the bidentate ligand of this type also is used for the hydroformylation of butadiene.
Though mentioned phosphorus organic compound is the good ligand of rhodium hydroformylation catalysts; but ligand or catalyst system have higher sensitiveness, and this can cause catalyst system or employed part to decompose relatively apace usually or oxidation at (simultaneously in the presence of industrial inevitable trace oxygen or peroxide) under the condition of most carbonylation.
In commercial run, getting rid of fully of oxygen is difficult.Usually, starting olefin and synthesis gas contain a spot of oxygen and/or oxygenatedchemicals.Because catalyst concn is owing to usually be low in the carbonylation that the high price of catalyst is carried out in industry, even a spot of oxygen of introducing with initiation material is for the stability of part or metal complex catalysts with active big adverse effect arranged also.This can cause the minimizing of space-time yield, optionally the more high flow rate of decline or catalyst.
Therefore the objective of the invention is to develop a kind of carbonylation method, it is characterized in that,, also do not have one or more in the above-mentioned shortcoming even when the initiation material of the common industrial quality of use.
Find surprisingly that now the deactivation of catalyst system can not have the secondary amine of hydrogen atom to reduce directly being bonded on two carbon atoms of nitrogen-atoms by adding secondary sterically hindered amines during carbonylation.
Therefore the present invention provides a kind of carbonylation method, at least a in the method can in the presence of the metal complex catalysts (this catalyst organic phosphorus compound is as part) of periodic table of elements VIII subgroup metal, the reaction by the compound of carbon monoxide carbonylation and carbon monoxide, it is characterized in that carbonylation is to carry out in the presence of the secondary sterically hindered amines with following general structure I:
Ra wherein, Rb, Rc, Rd, Re is identical or different alkyl with Rf, they can be together connected to each other.
The present invention similarly provides a kind of mixture, and this mixture comprises organic phosphorus compound as the metal complex catalysts of the VIII subgroup metal of the periodic table of elements of part and the secondary sterically hindered amines with following general structure I:
Figure BYZ000003949305500032
Ra wherein, Rb, Rc, Rd, Re is identical or different alkyl with Rf, they can be together connected to each other.
Method of the present invention has the following advantages: the stability of catalyst system is improved significantly, especially for oxidation sensitive and/or hydrolysis sensitiveness.Because improved oxidation sensitive might be used and contain the initiation material of a spot of oxygen as impurity.In addition, reaction process is fairly simple, because 100% eliminating of oxygen no longer is indispensable.Because the improved heat endurance of part, this carbonylation can carry out under higher temperature, observes the quick decomposition of part this moment under the situation of not adding stabilizing agent according to the present invention.The possibility of carrying out carbonylation under higher temperature makes it possible to improve reaction rate.
Method of the present invention utilizes the following examples to describe, but the invention is not restricted to these embodiments.The person skilled in the art can design other modification that belongs to theme of the present invention equally, and scope of the present invention is defined by specification and claim.
In carbonylation method of the present invention, can in the presence of the metal complex catalysts (it contains phosphorus organic compound (compound that especially has at least one phosphorus-to-oxygen bonds) as part) of periodic table of elements VIII subgroup metal, be reacted by at least a compound of carbon monoxide carbonylation and carbon monoxide, this carbonylation method is characterised in that carbonylation is to carry out in the presence of the secondary sterically hindered amines with following general structure I:
Figure BYZ000003949305500041
Ra wherein, Rb, Rc, Rd, Re is identical or different alkyl with Rf, they can be together connected to each other.The secondary sterically hindered amines used as stabilizers of general formula I.
In the method for the invention, the preferred use has 2,2,6,6-tetramethyl piperidine unit II or 2,2,6, and the secondary amine of 6-tetramethyl piperidine itself:
Figure BYZ000003949305500042
Preferred especially the use has 2,2,6, and the 6-tetramethyl piperidine unit and the latter are substituted and have the amine of general structural formula II a on 4:
Figure BYZ000003949305500043
Wherein R is an organic group, hydroxyl or halogen.Organic group R can be, for example, via hetero atom for example oxygen atom be bonded in organic group on the construction unit II ':
Figure BYZ000003949305500051
Especially, this organic group can have polymer architecture or have 1 to 50 carbon atom and also have heteroatomic organic group if necessary.This organic group especially preferably has carbonyl, for example ketone group, ester group or amide groups.Organic, optionally contain heteroatomic group and can especially have the replacement of 1-50 carbon atom or unsubstituted aliphatic series, alicyclic, aliphatic-alicyclic, heterocycle family, aliphatic series-heterocycle family, aromatics, aromatics-aromatics or aliphatic-aromatic alkyl, wherein the alkyl of Qu Daiing can carry substituting group, this substituting group is selected from primary, the second month in a season or tertiary alkyl, aliphatic group, aromatic group ,-N (R 1) 2,-NHR 1,-NH 2, fluorine, chlorine, bromine, iodine ,-CN ,-C (O)-R 1,-C (O) H or-C (O) O-R 1,-CF 3,-O-R 1,-C (O) N-R 1,-OC (O)-R 1And/or-Si (R 1) 3, R wherein 1It is the monovalence alkyl that preferably has 1 to 20 carbon atom.If there are a plurality of alkyl R 1, then these alkyl can be identical or different.Described substituting group preferably is confined to not have for reaction itself substituting group of influence.Particularly preferred substituting group can be selected from halogen such as chlorine, bromine or iodine, alkyl such as methyl, ethyl, propyl group, isopropyl, butyl, sec-butyl, the tert-butyl group, neopentyl, sec-amyl, tertiary pentyl, iso-octyl, uncle's octyl group, the 2-ethylhexyl, different nonyl, isodecyl or octadecyl, aryl such as phenyl, naphthyl or anthryl, alkylaryl such as tolyl, xylyl, 3,5-dimethylphenyl, the diethyl phenyl, trimethylphenyl, triethyl group phenyl or to alkyl phenyl, aralkyl such as benzyl or phenylethyl, alicyclic group such as cyclopenta, cyclohexyl, the ring octyl group, cyclohexyl ethyl or 1-methylcyclohexyl, alkoxyl such as methoxyl group, ethyoxyl, propoxyl group, butoxy or amoxy, aryloxy group such as phenoxy group or naphthoxy ,-OC (O) R 1Or-C (O) R 1For example acetyl group, propiono, trimethyl acetoxyl, triethyl group acetoxyl group or triphenyl acetoxyl group and carry the silicyl (Si (R of three alkyl 1) 3), for example trimethyl silyl, triethylsilyl or triphenyl silicyl.Particularly preferably be and carry, also have maximum one outside the 6-tetramethyl piperidine structural unit, very particularly preferably do not have other-N (R except 2,2,6 1) 2,-NHR 1And/or-NH 2Those groups of group are as the compound of the general formula I Ia of radicals R.
As the secondary amine of construction unit, very particularly preferably can use compound with structural formula II b to IIg shown below or their derivative with general formula I I.
Figure BYZ000003949305500061
N=1 to 20 wherein, preferred 1 to 10
Figure BYZ000003949305500062
N=1 to 12 wherein, preferred 8
Figure BYZ000003949305500063
N=1 to 17 wherein, preferred 13
Figure BYZ000003949305500071
The compound of structural formula II is known as HALS (hindered amine as light stabilizer) usually and is used to make polymer stabilising to resist by wearing out that light causes.Many publications (Pieter Gijsman, PolymerDegradation and Stability 43 (1994) 171-176; Peter P.Klemchuck, MatthewE.Gande, Polymer Degradation and Stability 22 (1988) 241-74; Peter P.Klemchuck, Matthew E.Gande, Makromol.Chem., Macromol.Symp.28,117-144, (1989)) refer to the mechanism of polymer stabilising, but still do not provide conclusive explanation so far.The compound of structural formula II is commercially available and can be for example from ICI America, Sigma-Aldrich, and Fluka, ABCR, Ciba, BASF and Degussa company obtain.The preparation example of these compounds is as being described in Polymers﹠amp; Polymer Composites, 8 volumes, No.4 is in 2000.
Secondary sterically hindered amines I preferably is 0.1: 1 to 100: 1, more preferably was used for reactant mixture in 2: 1 to 50: 1 according to the molar ratio with catalyst metals.It can be for example be introduced in the hydroformylation reaction device with the catalyst solution of starting olefin and/or recirculation.Amine preferably is introduced in the reaction with part.Preferably, in the storage process of part or composition catalyst, promptly added the compound of the structural formula II that is suitable as secondary amine.
Should be noted that, specifically in hydroformylation, might use the N-oxyl and the N-hydroxy compounds of deriving to replace secondary sterically hindered amines itself, because they are reduced into secondary sterically hindered amines under reaction condition from secondary sterically hindered amines.
The carbonylation method of the present invention preferably trivalent iron compound of the element (nitrogen, phosphorus, arsenic, antimony, bismuth) of the V main group by using the periodic table of elements carries out as part.Especially, use the three valent phosphors organic ligand.
As the phosphorus organic ligand, might use compound for example shown below or contain the compound of functional group shown at least one.
The compound of formula III
PR 2R 3R 4 III
Only have as radicals R 2To R 4All be bonded in organic group on the phosphorus atoms, for example phosphine or phosphine groups via carbon atom.
The compound of formula IV
PR 2R 3(TR 5) IV
Have as radicals R 2And R 3Whole via carbon atom be bonded on the phosphorus atoms organic group and as radicals R 5Be bonded in organic group on the phosphorus atoms via being selected from hetero atom T in oxygen or the nitrogen.For the situation of T=oxygen, this compounds for example is phosphinate or phosphinic acids foundation group.
The compound of formula V
PR 2(TR 5)(TR 6) V
Have as radicals R 2Via carbon atom be bonded on the phosphorus atoms organic group and as radicals R 5And R 6Be bonded in organic group on the phosphorus atoms via being selected from hetero atom T in oxygen or the nitrogen respectively, wherein this hetero atom can be identical or different.When T was oxygen under each situation, this compounds for example was phosphinate or phosphonous acid foundation group.
The compound of formula VI
P(TR 5)(TR 6)(TR 7) VI
Have as radicals R 5To R 7Be bonded in organic group on the phosphorus atoms via being selected from hetero atom T in oxygen or the nitrogen, wherein this hetero atom can be identical or different.When T was oxygen under each situation, this compounds for example was phosphite ester or orthophosphite group.
In VI, T is oxygen, NH or NR at structural formula II I 8Radicals R 2To R 8Be identical or different organic groups, they have 1 to 50 carbon atom and can be connected with each other.
As mentioned above, especially may use in addition in the method for the invention III to the compound with two or more functional groups of VI group as part.
If have compound, then radicals R with two functionalized phosphorus organic groups 2To R 7In one be divalence (referring to, for example, formula VIIb, wherein this radicals R 2Be divalence).It connects two functional groups and can belong among both any.For the compound with three functionalized phosphorus groups, radicals R 2To R 7In one be trivalent or radicals R 2 to R7 in two be divalence.Multivalence group high-ranking military officer can roll into a ball and be connected to each other.Analogue is applicable to the compound of the phosphorus organic group that has more than three.
The compound of the general type of this type of difunctionality phosphorus organic compound for example is: two phosphines (bond of III and III), bisphosphinic acid salt (the bond of IV and IV, when T is oxygen atom under each situation), biphosphinate (the bond of V and V, when whole T are oxygen atom) or bis-phosphite (bond of VI and VI is when whole T are oxygen atom).In addition, each functional group (III is to VI) can combine with another functional group (III is to VI), for example phosphinate-phosphinate (IV combines with V, when whole T are oxygen atom).Analogue is applicable to the compound of at least three kinds of phosphorus organic group dissimilar (III is to VI).
Carbonylation method of the present invention preferably carries out as the phosphorus organic ligand by the compound that uses following formula:
R 2[PR 3R 4] x， VII
The integer of x=1 to 10 wherein, preferred 1 to 4 and preferred especially 2, R 2=x valency organic group and R 3And R 4=organic group, wherein R 3And R 4Can be identical or different and can be with covalent keyed jointing each other, wherein when x 〉=2, [PR 3R 4] radicals R of construction unit 3And R 4Can be respectively different.In the method for the invention, the preferred especially at least a compound that is selected among formula VIIa, VIIb and the VIIc of using is as the phosphorus organic ligand:
R 2[PR 3R 4] VIIa
[R 3R 4P]R 2[PR 3R 4] VIIb
[R 3R 4P]R 2[PR 3’R 4’] VIIc
R wherein 3, R 4, R 3' and R 4'=organic group, wherein R 3And R 3' and/or R 4And R 4' be different, and radicals R 3And R 4And R 3' and R 4' can be identical or different and can be with covalent keyed jointing each other.The compound of formula VIIb is phosphorus organic group-[PR wherein 3R 4] special case of compound of all identical formula VIIc.Radicals R 2, R 3, R 4, R 3' and R 4' preferably do not have hetero atom and for example maybe can have oxygen or sulphur as heteroatomic organic group.This radicals R 2, R 3, R 4, R 3' and R 4' especially preferably be bonded in the organic group on the phosphorus or be bonded in organic group (especially alkyl) on the phosphorus via carbon atom via hetero atom (preferred oxygen or nitrogen).
The possible compound of the part of formula VII is a phosphine, phosphinate, phosphinate or phosphite ester, when having two or more phosphorus organic group, be bis-phosphite or polyphosphite maybe, bisphosphinic acid ester or repeatedly phosphonate ester or biphosphinate or many phosphinates or have the part of two or more different phosphate organic groups, for example phosphinate-phosphinate, phosphinite-phosphite or phosphinate-phosphite ester.Radicals R 2, R 3, R 4, R 3' and R 4' therefore preferably directly or via oxygen atom being bonded in organic group on the phosphorus, especially can be substituted or unsubstituted alkyl.The part of formula VII preferably is not phosphoramidite (Phosphoramidit) compound.
Replacing trialkyl phosphine or triaryl phosphine compound is particularly suitable in the method for the present invention as the phosphine part.Preferably the phosphine part is, for example, replaces or unsubstituted triphenylphosphine, and especially wherein at least one in the middle of phenyl carried the triphenylphosphine of sulphonic acid ester (salt) group.Particularly preferred phosphine is selected from: triphenylphosphine, three (p-methylphenyl) phosphine, three (tolyl) phosphine, three (o-tolyl) phosphine, three (p-methoxyphenyl) phosphine, three (to dimethylamino phenyl) phosphine, tricyclohexyl phosphine, three cyclopenta phosphines, triethyl phosphine, three (1-naphthyl) phosphine, tribenzyl phosphine, tri-n-butyl phosphine, tri-butyl phosphine.
Common phosphinate part is described in US-A-5 especially, 710,344, WO-A-95/06627, US-A-5,360,938 or JP-A-07-082281 in.Example is diphenyl (phenoxy group) phosphine and its derivative, and wherein hydrogen atom is all or part of by alkyl and/or aryl or halogen atom replacement, diphenyl (methoxyl group) phosphine and diphenyl (ethyoxyl) phosphine.
As the phosphinate part, might use to have at least two organic group and whole parts via the organic group of carbon atom keyed jointing via the oxygen atom keyed jointing, wherein two or more in these groups can be each other with the covalent keyed jointing.The example that can be used in the phosphinate in the method for the present invention is a methyl diethoxy phosphine, phenyl dimethoxy phosphine, phenyl two phenoxy group phosphines, 2-phenoxy group-2H-dibenzo [c, e] [1,2] oxaphosphorin and their derivative, wherein hydrogen atom is all or part of by alkyl and/or aryl or halogen atom replacement, with be described in WO-A-98/43935, among JP-A-09-268152 and the DE-A-198 10 794 and the part in German patent application DE-A-199 54 721 and DE-A-199 54 510.Being particularly suitable for method of the present invention is for example explained by the general formula that is disclosed among the DE-A-199 54 721 with the part that is particularly suitable for hydroformylation.The phosphinate part that very particularly preferably is used for method of the present invention is to be selected from the part of formula VIIa-1 in the compound of VIIa-24:
Figure BYZ000003949305500101
Figure BYZ000003949305500111
Phosphite ester is the most suitable part that is used for method of the present invention.Trialkyl phosphite that replaces or triaryl phosphites compound are especially suitable for use as the phosphite ester ligand in the method for the present invention.Particularly preferred phosphite ester ligand is, for example, replaces or unsubstituted triphenyl phosphite, and especially wherein at least one in the phenyl carried the triphenyl phosphite of sulfonate ester group.The example of phosphite ester is: Trimethyl phosphite, triethyl phosphite, tricresyl phosphite n-propyl, triisopropyl phosphite, tri-n-butylphosphite, tricresyl phosphite isobutyl ester, the tricresyl phosphite tert-butyl ester, tricresyl phosphite (2-ethylhexyl) ester, triphenyl phosphite, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, tricresyl phosphite (the 2-tert-butyl group-4-methoxyphenyl) ester, tricresyl phosphite (the 2-tert-butyl group-4-aminomethyl phenyl) ester, tricresyl phosphite (p-methylphenyl) ester.In addition, especially be described in EP-A-1 555 08, US-A-4,668,651, US-A-4,748,261, US-A-4,769,498, US-A-4,774,361, US-A-4,835,299, US-A-4,885,401, US-A-5,059,710, US-A-5,113,022, US-A-5,179,055, US-A-5,260,491, US-A-5,264,616, US-A-5,288,918, US-A-5,360,938, EP-A-472 071, and the steric hindrance phosphite ester ligand among EP-A-518 241 and the WO-A-97/20795 is suitable part.
The possible part of formula VIIc is phosphite ester-phosphine compound, phosphite ester-phosphinate compound, phosphite ester-phosphinate compounds, phosphite ester-bi-ester of phosphite, phosphine-phosphine compound, phosphinate-phosphine compound, phosphinate-phosphine compound, phosphinate-phosphinate compounds, phosphinate-phosphinate compounds or phosphinate-phosphinate compound.The possible compound of the part of formula VIIb is two phosphines, bisphosphinic acid ester, biphosphinate or bis-phosphite.
Can be used in two phosphines in the method for the present invention and their preparation method for example is described among the WO 02/076996.Wherein described for method of the present invention preferred two phosphines be so two phosphines, wherein R 2Be bivalent substituted or unsubstituted alkyl aryl (CH 2-Ar-CH 2-) [R 4R 3P]-R 2-[PR 3' R 4'].Radicals R wherein 2Be the formula [R of divalent aryl Ar 4R 3P]-Ar-[PR 3' R 4'] two phosphines be suitable for method of the present invention equally.
The compound of formula VIIc can for example be a following compounds.
Figure BYZ000003949305500121
Figure BYZ000003949305500131
Wherein W, X, Y and Z are replacement or the unsubstituted aliphatic series with 1-50 carbon atom, alicyclic, aliphatic series-alicyclic, heterocycle family, aliphatic series-heterocycle family, aromatics-aromatics or aliphatic-aromatic alkyl, wherein W, X, Y and Z can be identical or different or with covalent keyed jointing each other, and wherein Q be have 1 to 50 carbon atom divalence at least, replacement or unsubstituted aliphatic series, alicyclic, aliphatic series-alicyclic, heterocycle family, aliphatic series-heterocycle family, aromatics, aromatics-aromatics or aliphatic-aromatic alkyl.Substituted hydrocarbon radical can have be selected from primary, the second month in a season or tertiary alkyl, alicyclic group, aromatic group ,-N (R 8) 2,-NHR 9,-NH 2, fluorine, chlorine, bromine, iodine ,-CN ,-C (O)-R 10,-C (O) H or-C (O) O-R 11,-CF 3,-O-R 12,-C (O) N-R 13,-OC (O)-R 14And/or-Si (R 15) 3In one or more substituting groups, R wherein 8To R 15Each preferably has the monovalence alkyl of 1 to 20 carbon atom naturally.If there are a plurality of alkyl R 8To R 15, then these alkyl can be identical or different.This substituting group preferably is confined to not have for reaction itself substituting group of influence.Particularly preferred substituting group can be selected from halogen such as chlorine, bromine or iodine, alkyl such as methyl, ethyl, propyl group, isopropyl, butyl, sec-butyl, the tert-butyl group, neopentyl, sec-amyl, tertiary pentyl, iso-octyl, uncle's octyl group, the 2-ethylhexyl, different nonyl, isodecyl or octadecyl, aryl such as phenyl, naphthyl or anthryl, alkylaryl such as tolyl, xylyl, 3,5-dimethylphenyl, the diethyl phenyl, trimethylphenyl, triethyl group phenyl or to alkyl phenyl, aralkyl such as benzyl or phenylethyl, alicyclic group such as cyclopenta, cyclohexyl, the ring octyl group, cyclohexyl ethyl or 1-methylcyclohexyl, alkoxyl such as methoxyl group, ethyoxyl, propoxyl group, butoxy or amoxy, aryloxy group such as phenoxy group or naphthoxy ,-OC (O) R 14Or-C (O) R 10, for example acetyl group, propiono, trimethyl acetoxyl, triethyl group acetoxyl group or triphenyl acetoxyl group and carry the silicyl (Si (alkyl) of three alkyl 3), for example trimethyl silyl, triethylsilyl or triphenyl silicyl.
The example that can be used as the compound of bis-phosphite in the method for the invention for example is described among the WO 02/00670, and " formula III " wherein mentioned (being different from the formula III in this patent text) compound is the compound corresponding to formula VIIb of the present invention.The narration of WO 02/00670 is introduced in the disclosure for reference.
The special shape of bis-phosphite is so-called pair of acyl group phosphite ester or acyl group phosphite ester-phosphite ester, and wherein following construction unit S occurs twice or once
Figure BYZ000003949305500141
Wherein A is bivalent substituted or the unsubstituted alkyl or the aryl that can form the member ring systems corresponding with construction unit S, and group L is to be bonded in organic group on the phosphorus atoms via oxygen or carbon atom.The specific examples of two acyl group phosphite esters for example has been disclosed among the WO 03/016320 as formula I and II (k=2 under each situation).Be disclosed in formula A among the WO 03/016320 to the compound of H corresponding to formula VIIb of the present invention, and the compound of WO 03/016320 Chinese style I to M be also can be in the method for the invention as the example of the compound of the formula VIIc of phosphorus organic ligand.The narration of WO03/016320 is introduced in the disclosure for reference.
The general example of the acyl group bi-ester of phosphite of formula VIIc is a following compounds:
Figure BYZ000003949305500142
Wherein X and Y are replacement or the unsubstituted aliphatic series with 1-50 carbon atom, alicyclic, aliphatic series-alicyclic, heterocycle family, aliphatic series-heterocycle family, aromatics-aromatics or aliphatic-aromatic alkyl, wherein X and Y can be identical or different or with covalent keyed jointing each other, Q is replacement or the unsubstituted aliphatic series that preferably has the divalence at least of 1 to 50 carbon atom, and is alicyclic, aliphatic series-alicyclic, heterocycle family, aliphatic series-heterocycle family, aromatics, aromatics-aromatics or aliphatic-aromatic alkyl, wherein substituted hydrocarbon radical has and is selected from-N (R 20) 2,-NHR 20,-NH 2, fluorine, chlorine, bromine, iodine ,-OH ,-CN ,-C (O)-R 20,-C (O) H or-C (O) O-R 20,-CF 3,-O-R 20,-C (O) N-R 20,-OC (O)-R 20And/or-Si (R 20) 3In substituting group, R wherein 20Preferably have the monovalence alkyl of 1-20 carbon atom and have a plurality of alkyl R if be 20, then these can be identical or different, and R 16To R 19Be independently from each other that monovalence replaces or unsubstituted aliphatic series, alicyclic, aromatics, heteroaromatic, mixed aliphatic series-alicyclic, mixed aliphatic series-aromatics, heterocycle family has the mixed aliphatic series-heterocyclic hydrocarbon group of 1-50 carbon atom, H, F, Cl, Br, I ,-CF 3,-CH 2(CF 2) jCF 3, j=0-9 wherein ,-OR 21,-COR 21,-CO 2R 21,-CO 2M ,-SR 21,-SO 2R 21,-SOR 21,-SO 3R 21,-SO 3M ,-SO 2NR 21R 22,-NR 21R 22,-N=CR 21R 22, R wherein 21And R 22Be independently from each other H, the monovalence with 1 to 25 carbon atom replaces or unsubstituted aliphatic series and aromatic hydrocarbyl, and M is an alkali metal ion, first alkaline-earth metal ions of form, ammonium ion or
Figure BYZ000003949305500151
Ion, or adjacent radicals R 16To R 19Form together to condense and replace or unsubstituted aromatics heteroaromatic, aliphatic series, mixing aromatic-aliphatic or mixing heteroaromatic-aliphatic member ring systems; Wherein substituted hydrocarbon radical has and is selected from-N (R 23) 2,-NHR 23,-NH 2, fluorine, chlorine, bromine, iodine ,-OH ,-CN ,-C (O)-R 23,-C (O) H or-C (O) O-R 23,-CF 3,-O-R 23,-C (O) N-R 23,-OC (O)-R 23And/or-Si (R 23) 3In substituting group, R 18Be preferably to have the monovalence alkyl of 1 to 20 carbon atom and work as to have a plurality of alkyl R 23The time, these can be identical or different, and radicals R 16, R 17, R 18And R 19Be identical or different.
The general formula that is preferably used as two acyl group bi-ester of phosphite of part is in the method for the invention provided by formula VIIb-1 and VIIb-2.
K=2 in the formula, R 16, R 17, R 18And R 19Has the meaning that provides for structural formula VIIc-9 to VIIc-11, Q is bivalent substituted or the unsubstituted aliphatic series with 1 to 50 carbon atom, and is alicyclic, mixed aliphatic series-alicyclic, heterocycle family, mixed aliphatic series-heterocycle family, aromatics, heteroaromatic, mixed aliphatic series-aromatic hydrocarbon radical, wherein the aliphatic series part of Q can contain aerobic, sulphur and/or nitrogen, and substituted hydrocarbon radical Q can have and R 16To R 19The substituting group of same meaning.The preparation of this compounds and other preferred embodiment can be seen in WO 03/016320, and its narrating content is introduced in the disclosure.
As the initial compounds for the treatment of carbonylation, for example might use in the method for the invention and be selected from alpha-olefin, internal olefin, cycloolefin, alefinically unsaturated compounds in alkenyl alkyl ethers and the alkenols, wherein these compounds can be that replace or unsubstituted separately.The example of suitable alpha-olefin compound is a propylene, butylene, amylene, butadiene, pentadiene, 1-hexene, 1-heptene, 1-octene, the 1-nonene, 1-decene, 1-endecatylene, 1-dodecylene, cetene, 2-ethyl-1-hexene, 1,4-hexadiene, 1,7-octadiene, 3-cyclohexyl-1-butylene, styrene, 4 vinyl cyclohexene, allyl acetate, vinyl formate, vinyl acetate, propionate, allyl methyl ether, vinyl methyl ether, EVE, allyl alcohol, 3-phenyl-1-propylene, oneself-1-alkene-4-alcohol, suffering-1-alkene-4-alcohol, acetate 3-butene esters, allyl propionate, allyl butyrate, the sad n-propyl of 7-, 7-octenoic acid, 5-hexene acid amides, 1-methoxyl group-2,7-octadiene and 3-methoxyl group-1,7-octadiene.If method of the present invention is a hydroformylation, treat that then the initial compounds of carbonylation preferably is selected from alkene or alkene mixture.Especially can use to have 3 to 24, preferred 4 to 16, preferred especially 3 to 12 carbon atoms and monoolefine terminal or the two keys of inner C-C, for example 1-or 2-amylene, 2-methyl-1-butene alkene, 2-methyl-2-butene, 3-methyl-1-butene, 1-, 2-or 3-hexene, the C that when propylene dimerization, forms 6-alkene mixture (propylene dimer), heptene, 2-or 3-methyl isophthalic acid-hexene, octene class, 2-methyl heptene class, 3-methyl heptene class, 5-methyl-2-heptene, 6-methyl-2-heptene, 2-ethyl-1-hexene, the isomery C that when butene dimerization, forms 8-alkene mixture (dibutene), nonene, 2-or 3-methyl octene, the C that when the propylene trimerization, forms 9-alkene mixture (tripropylene), decene, 2-ethyl-1-octene, dodecylene, the C that forms during poly-or butylene trimerization at propylene four 12-alkene mixture (polypropylene tetramer or three polybutene), tetradecene, hexadecene, the C that when butylene four gathers, forms 16-alkene mixture (four polybutene) and by the common oligomeric prepared alkene mixture of the olefines of the carbon atom with varying number (preferred 2 to 4), if the suitable cut that after fractionation, obtains having identical or similar chain length.Might use the alkene produced by Fischer-Tropsch synthesis or alkene mixture equally and by the alkene of the oligomeric acquisition of ethene or the alkene that can obtain via metathesis reaction.Preferred initiation material is C 4-, C 8-, C 9-, C 12-or C 16-alkene mixture.
Except that carbon monoxide and treat to be selected from hydrogen the initial compounds of carbonylation, water, at least a compound in amine or the alcohol can be in the method for the invention as additional reactant.Except carbon monoxide and treating the initial compounds of carbonylation, also especially preferably use hydrogen as additional reactant at least, for example, hydrogen can use and carries out hydroformylation reaction with the form of synthesis gas.
Method of the present invention can be undertaken by using various catalyst and/or part.
Possible catalytically-active metals is the metal of periodic table of elements VIII subgroup, rhodium for example, and cobalt, platinum or ruthenium especially preferably use cobalt or the rhodium metal as the VIII subgroup of the periodic table of elements.
The active catalyst complex that is used for carbonylation be by the salt of metal or compound (catalyst precarsor), part, carbon monoxide and if applicable other reactant (for hydroformylation, being hydrogen) form.This advantageously in carbonylation processes (that is, for example, in hydroformylation process) original position carry out.Common catalyst precarsor is, for example, and caprylate or acetyl pyruvate.
If method of the present invention is a hydroformylation, this preferably carries out according to known method, for example at J.FALBE, " New Syntheses with Carbon Monoxide "; SpringerVerlag, Berlin, Heidelberg; New York is below the 95th page, described in (1980).
The molar ratio of metal and part preferably 0.1/1 to 1/1000, more preferably 1/1 to 1/100 and preferred especially 1/1 to 1/50.Preferably by using the phosphorus organic ligand to carry out according to the certain mol proportion rate of phosphorus organic ligand and metal, this ratio makes part also be present in the reactant mixture as free part to carbonylation method of the present invention.Concentration of metal is in 1ppm (quality) arrives 1000ppm (quality) scope in reactant mixture, preferably in 5ppm (quality) arrives 300ppm (quality) scope.
Fresh part can be added in the reaction at any time, so that keep the constant concentration of free ligand.Before using, can synthesize transition metal compound catalizer.Yet the catalytic activity complex generally is to form from catalyst precarsor and phosphorus organic ligand in reaction medium on the spot.
For hydroformylation, preferably 60 ℃ to 180 ℃ of reaction temperatures in the method for the invention, more preferably 90 ℃ to 150 ℃, pressure is 1 to 300 crust preferably, more preferably 15 to 60 crust.Synthesis gas when being used for hydroformylation, the molar ratio (H of hydrogen and carbon monoxide 2/ CO) preferably 10/1 to 1/10 and more preferably 1/2 to 2/1.
Catalyst, promptly metal and part preferably are dissolved in the carbonyl mixture of being made up of initiation material (alkene) and product (aldehyde, alcohol, higher-boiling compound) equably.Can randomly use solvent in addition, toluene for example, Texanol, Diphyl (the low eutectic mixture of biphenyl and diphenyl ether), high boiling residue, phthalate such as phthalic acid two (2-ethylhexyl) ester or dinonyl phthalate, or 1, the ester of 2-cyclohexane cyclohexanedimethanodibasic.
If carbonylation according to the present invention is a hydroformylation, this can carry out continuously or off and on.Wherein the example of the commercial plant that can react is the stirring-type container, bubble column, and the nozzle-type reactor, tubular reactor and annular reactor, some in them can be cascades and/or be equipped with internals.
This reaction can be carried out in one or more stages.Formed aldehyde compound and catalyst separate can by conventional method for example fractionation carry out.In industry, this can for example pass through the way of distillation, carries out by means of falling film evaporator or thin film evaporator.This was useful especially when the catalyst in being dissolved in high boiling solvent separated from low boiling product more.Isolated catalyst solution, wherein the secondary amine of the employed general formula I of major part preferably also exists, and can be used in further hydroformylation.When using light alkene (for example propylene, butylene, amylene), it also is possible discharging product via gas phase from reactor.
Wherein only lose the carbonylation of a spot of part or catalyst system, especially hydroformylation reaction can be carried out by means of method of the present invention.Except substituting caused more low-cost of part or catalyst system itself, also generated minor by-products caused and that need remove in addition in the method for the invention by the decomposition of part.
When carrying out method of the present invention, obtain or use a kind of mixture, this mixture comprise contain the phosphorus organic compound as part, the metal complex catalysts of periodic table of elements VIII subgroup metal and secondary sterically hindered amines with following general structural formula I,
Figure BYZ000003949305500181
Ra wherein, Rb, Rc, Rd, Re is identical or different alkyl with Rf, they can be together connected to each other.Preferably comprise according to mixture of the present invention and to have 2,2,6, the amine of 6-tetramethyl piperidine unit II
Figure BYZ000003949305500191
As secondary amine.
Especially, described mixture can comprise above-mentioned secondary amine, especially those of structural formula II a.Mixture of the present invention especially preferably comprises the compound that is selected from structural formula II b to IIg or at least a compound in their derivative as secondary amine:
Figure BYZ000003949305500192
N=1 to 20 wherein, preferred 1 to 10
N=1 to 12 wherein, preferred 8
Figure DEST_PATH_GSB00000006453700012
N=1 to 17 wherein, preferred 13
Figure DEST_PATH_GSB00000006453700013
Mixture of the present invention preferably comprise formula III at least a compound of VI or contain formula III to the compound of at least two functional groups of VI as the phosphorus organic ligand.Mixture of the present invention more preferably comprises the compound of formula VIIa, VIIb or VIIc as the phosphorus organic ligand.Mixture of the present invention especially preferably comprises formula VIIc-9, at least a compound of VIIc-10 or VIIc-11, and very particularly preferably at least a compound of formula VIIIb-1 or VIIb-2 is as the phosphorus organic ligand.
In mixture of the present invention, the phosphorus organic ligand preferably according to and metal between 0.1: 1 to 100: 1, more preferably 1: 1 to 50: 1 molar ratio exists.Mixture can comprise the metal of above-mentioned metal as periodic table of elements VIII subgroup.Yet mixture preferably comprises cobalt or the rhodium metal as periodic table of elements VIII subgroup.
The secondary amine compound of general formula I preferably according to and catalyst metals between from 0.1: 1 to 100: 1 molar ratio, more preferably, be present in the mixture of the present invention according to from 2: 1 to 50: 1 molar ratio.
Mixture of the present invention can be only by metal complex catalysts, and the secondary amine of free phosphorus organic ligand and general formula I is formed if necessary.Except that these components, mixture of the present invention preferably also comprises other component, for example at least a solvent, initiation material, product, catalyst precarsor or the product that forms from catalyst or catalyst precarsor.Solvent can be any material of performance inertia in the reaction of using compound of the present invention.If mixture of the present invention is used as catalyst solution in carbonylation method (especially hydroformylation process), the product that then advantageously uses carbonylation for example the aldehyde product as solvent.This feasible unnecessary pollution that might avoid product.Yet mixture of the present invention will also be understood that the reactant mixture that is obtained when using above-mentioned catalyst complexes and stabilizing agent.
The following example is used to illustrate the present invention but does not limit the scope of the invention, and scope of the present invention is to be defined by specification and claim.
Embodiment:
Embodiment 1: the preparation of the part that uses
In this embodiment, at first be described in the preparation method of the ligand i X that uses among the embodiment 2.
Figure BYZ000003949305500211
Ligand i X (VIIc type)
The out of Memory relevant with the preparation of intermediate as described below and part also can be referring to for example J.Mol.Cat., and 1983,83,17 and US 4,885,401.Similarly the preparation example of part is as being described among the EP 1 201 675.The preparation example of chloronaphthyl, methylnaphthyl two oxa-phosphorus heterocycle hexanone (Chloro-naphthyldioxaphosphorinon) analogs is as also being described among the BE667036.
Embodiment 11:2, the preparation of 2 '-two (3, the 5-di-t-butyl) phenol (L002)
Reaction equation:
Figure BYZ000003949305500221
The methyl alcohol of 2l joined precision glass agitator (polytetrafluoroethylene (PTFE) dasher) is housed, the inside temperature measurement device, the inlet tube (air is used) that the sintered glass material is arranged is in the 4l reaction flask of reflux condenser and outlet (" bubbler " arranged in blast pipe).Then under strong agitation with 2 of 1000g (4.85mol), 4-two-tert-butyl phenol is dissolved in wherein.With the copper chloride dihydrate of 4g (23.5mmol) and the N of 4mL (26.5mmol), N, N ', N '-tetramethylethylenediamine adds in this agitating solution subsequently.Reaction solution at room temperature stirs then, simultaneously bubbling air (can be distinguished by violent " bubbling ").The small loss of solvent compensates by replenishing methyl alcohol.In order to compensate the loss that the evaporation that caused by " extracting " causes, after the long reaction time, add the N of other 4ml, N, N ', N '-tetramethylethylenediamine.In the duration of experiment, product precipitum as light color from glaucous reaction solution is precipitated out.
For post processing, the salt of precipitation is come out by suction filtration.It is then with the 100ml methanol wash 3 times that has been cooled to 0 ℃.Salt subsequently large tracts of land be distributed on the metal dish and in vacuum drying oven in 55 ℃ of dryings 24 hours.Yield is about 70%.Purity is greater than 99% (quality).
Embodiment 1.2: from 2, and 2 '-two (3, the 5-di-t-butyl) phenol (L002) preparation torak acid esters (L008_01)
Reaction equation:
Figure BYZ000003949305500222
Carry out following experiment by using the protective gas technology.Two phenyl compound L002 of weighing 411g (0.1mol) join in the fixing 500ml Schlenk container.The Schlenk container of loading is evacuated and feeds argon gas subsequently.When stirring, dry toluene and the utilization of adding 200mL are the dry triethylamine of 46mL with the syringe interpolation 33.4g (0.33mol) of argon gas purge in advance, dissolving then.In order to dissolve two phenyl compounds, slight warm (using hand) needs.
The dry toluene of 200mL joined in the fixing 1L Schlenk container and the phosphorus trichloride (utilizing the syringe of being crossed by the argon gas purge to add) of 13.8g (0.1mol)=8.8mL is dissolved in wherein.Previously prepared glycol/toluene/triethylamine mixture utilizes siphon pipe to be added dropwise in this solution, stirs under-5 ℃ to 0 ℃ temperature simultaneously.If chloride precipitation and make the stirring of the mixture difficulty that becomes then adds additional solvent at this moment.Reactant mixture rises to room temperature a night by leaving standstill then.The ammonium chloride that is obtained utilizes the sintered glass material to be filtered off subsequently, and filter cake washs with the dry toluene of 2 * 50mL.
For further post processing, by the cold-trap that has used by cooled with liquid nitrogen, in the oil pump vacuum at room temperature from the filtrate distilling off solvent.The torak acid esters that is obtained is analyzed and is stored in the glove box.Yield is about 90%, and purity is measured greater than 99% (quality) by GC/MS.
Embodiment 1.3: by the prepared in reaction ligand L 037_01 of torak acid esters (L008_01) and 2,2 '-two (3, the 5-di-t-butyl) phenol (L002)
Reaction equation:
Figure BYZ000003949305500231
Carry out following experiment by using the protective gas technology.Two phenyl compound L002 of weighing 41.1g (0.1mol) join in the fixing 1l Schlenk container.The Schlenk container is evacuated and feeds argon gas subsequently.Add the dry toluene of 350mL and utilize the dry triethylamine of adding 12.2g (0.12mol)=16.8mL in advance with the syringe of argon gas purge, strong agitation dissolving then.In order to dissolve two phenyl compounds, slight warm (using hand) needs.
Then in glove box among protective gas, the torak acid esters L008_01 of weighing 47.5g (0.1mol) joins in the fixing 250ml Schlenk container.Dry toluene with 200mL charges in the Schlenk container subsequently, and this salt under agitation dissolves.The solution that is obtained utilizes siphon pipe to be added dropwise in glycol/toluene/triethylamine solution under about-10 ℃ temperature.Reactant mixture rises to room temperature a night by leaving standstill then.Mixture is heated to 80 ℃ and kept 1 hour then under this temperature.To transform in order testing fully, to allow ammonium chloride carry out sedimentation and carry out GC/MS for supernatant liquor and analyze.If this analysis showed that also not reaction fully of initiation material, then under 80 ℃, heated 1 hour once more.According to the GC/MS test initiation material that utilizes noted earlier, repeat this program if necessary once more then.The ammonium chloride of precipitation leaches on the sintered glass material subsequently, and filter cake washs with the dry toluene of 2 * 50mL then.
For further post processing, by the cold-trap that has used by cooled with liquid nitrogen, in the oil pump vacuum at room temperature from the filtrate distilling off solvent.The crude product that is obtained washs with the dry acetonitrile of about 500ml.The salt of purifying is separated by filtering on the sintered glass material, and with the dry acetonitrile washed twice of 50ml, drying is analyzed and is stored in the glove box.Yield is about 70%, by 31The purity that P-NMR measures is greater than 97% (quality).
Embodiment 1.4: form chloronaphthyl, methylnaphthyl two oxa-phosphorus heterocycle hexanones (Chlor-naphthyldioxaphosphorinon) by 1-hydroxyl-2-naphthoic acid and phosphorus trichloride reaction and prepare ligand L 062_01
Reaction equation:
Figure BYZ000003949305500241
Carry out experiment as described below by using the protective gas technology.1-hydroxyl-2-naphthoic acid of weighing 18.9g (0.1mol) joins in the fixing 500ml Schlenk container.This Schlenk container is evacuated subsequently, utilizes hair dryer to be heated to the degree of hand sensible heat, after cooling, feeds argon gas then.The dry toluene of 250ml is added with siphon pipe, stir this mixture then tempestuously.
The dry toluene of 100mL is joined in second fixing 250ml Schlenk container.When stirring, utilize the syringe of having crossed with the argon gas purge to inject the triethylamine of 30.7g (0.3mol)=42.2ml and the phosphorus trichloride of 13.9g (0.1mol)=8.8ml respectively then.In vigorous stirring, at room temperature, the solution that is obtained is joined in this naphthoic acid solution by part with siphon pipe through 1.5 hours time.In the interpolation process, this acid is dissolved at leisure and is formed insoluble ammonium chloride (suspension reaction).Reactant mixture is stirred to morning next day subsequently.
Can not carry out the conversion test in embodiment 1.3, carried out at this moment, because the also not suitably sedimentation of a large amount of ammonium chloride.Ammonium chloride at first leaches on the sintered glass material then, uses the dry toluene washed twice of 100ml then.Subsequently at carrying out GC/MS on the filtrate that is obtained, to check this conversion.
In order to measure the quality of torak acid esters, the cold-trap that whole toluene has been filled liquid nitrogen by use utilizes the oil pump vacuum at room temperature to be separated, and the remaining product of weighing.For further processing, the torak acid esters of ormal weight utilizes stirring action to be dissolved in the dry toluene of 300ml, is stored in refrigerator till the further use then.Yield is about 90%, and the purity of measuring by means of GC/MS is greater than 99% (quality).
Embodiment 1.5: by two organic phosphite hydroxide (L037_01) and chloronaphthyl, methylnaphthyl two oxa-phosphorus heterocycle hexanone (L062_01) prepared in reaction ligand i X
Reaction equation:
Figure BYZ000003949305500251
Carry out experiment as described below by using the protective gas technology.The two organic phosphite hydroxide L037_01 of weighing 42.5g (0.05mol) join in the fixing 500ml Schlenk container.Add the dry toluene of 200mL subsequently and utilize the triethylamine that adds 11.2g (0.11mol)=15.5mL in advance with the syringe of argon gas purge, stirring and dissolving then.In vigorous stirring, this soln using siphon pipe is added dropwise to the L062_01[0.06mol (the torak acid esters has excessive a little) of the embodiment 1.4 that institute's content of calculating, measuring is housed under 0-4 ℃ temperature] the fixed 1000ml Schlenk container of starting soln in.Reactant mixture is subsequently through rising to room temperature a night.In morning next day, formed ammonium chloride generation sedimentation and from supernatant liquor, obtain the sample [test of the conversion of initiation material (fragment L037_01)] that is used for GC/MS.If initiation material is not reaction fully also, then this mixture heated 2 hours down at 60 ℃.According to method noted earlier, utilize GC/MS to carry out the test of the existence of relevant initiation material then.Formed ammonium chloride leaches on the sintered glass material then, and filter cake washs with the dry toluene of 2 * 50mL.
For post processing,, utilize oil pump vacuum distilling off solvent from filtrate at room temperature by using the cold-trap of filling liquid nitrogen.The crude product that is obtained washs with the dry acetonitrile of about 400ml.Cleaning solution utilizes the sintered glass material to separate, and the salt of purification washs with the dry acetonitrile of 2 * 50ml, and drying is analyzed and is stored in the glove box.Yield is about 70%, by 31The purity that P-NMR measures is greater than 99% (quality).
Embodiment 2: the hydroformylation experiment
Utilize the validity of the autoclave test stable testing agent that repeats.Program is as follows:
In the 300ml autoclave, experimentize.Autoclave carries out electrical heating and can operate under about 150 ℃ at the most temperature.Pressure utilizes the Bronkhorst pressure regulator to keep constant.Autoclave can be operated under the pressure of 6MPa at the most.Autoclave is equipped with agitator and sampling facility in addition.
In embodiment 2.1 to 2.4, in autoclave, n-nonanoic acid rhodium that will about 23mg under each situation and the ligand i X (from embodiment 1) of 0.31g add in four butane of about 75g.Add stabilizing agent with tangible molar excess for rhodium (about 10 to 20 times excessive).
Catalyst is about 2.5 hours of pre-activation in synthesis gas under 120 ℃ and 5 crust, then pressure is set to 2MPa and adds the 1-octene of about 75g via heatable gas cylinder.Hydroformylation carried out 2 hours.Reactant mixture is depressurized then, and cool to room temperature covers with argon gas, joins then in the top of falling film evaporator.Falling film evaporator is in 18hPa and 120 ℃ of operations down.Under these conditions, aldehyde is separated.Obtain catalyst solution in the bottom of falling film evaporator, after the quantity of solvent that compensation is lost, this solution is recycled to then and is used for reaction process in the autoclave.The periodicity of being realized before the conversion of olefines rate reduces is the measuring of validity of stabilizing agent.
Embodiment 2.1 (contrast experiment): the hydroformylation (experiment 1104) that does not have stabilizing agent
According to carrying out the experiment of embodiment 2.1 in method described in the embodiment 2.Promptly dropped to 14.24% at the second period conversion ratio.
Table 1: the experimental result in embodiment 2.1
Figure BYZ000003949305500271
Embodiment 2.2 (according to the present invention): the hydroformylation (experiment 1126) that uses two (2,2,6, the 6-tetramethyl-piperidyl) esters of stabilizing agent decanedioic acid
In this experiment, add the stabilizing agent (two (2,2,6, the 6-tetramethyl-piperidyl) esters of stabilizing agent decanedioic acid) of 0.5475g.Evaporator temperature is 125 ℃.Set equally among all the other full terms and the embodiment 2.1.Obtain following result: reach 14 cycles.Conversion ratio is reduced to about 29% from 79%.Aldolize, be hydrogenated to pure and mild hydrogenation of olefin and work hardly.Based on the results are shown in the table 2 of each cycle.
The experimental result of table 2: embodiment 2.2
Embodiment 2.3 (according to the present invention): experiment 1127
Experimentize according to the mode identical with embodiment 2.2, just evaporator temperature is brought up to 130 ℃.The results are shown in the table 3.Reach 14 cycles again.Conversion ratio is reduced to 38.0% from 82.9%.Aldolize, aldehyde are hydrogenated to pure and mild olefin hydrogenation and become alkane inoperative equally here.
The experimental result of table 3: embodiment 2.3
Figure BYZ000003949305500281
Embodiment 2.4 (according to the present invention): experiment 1128
Experimentize according to the mode identical with embodiment 2.3, just evaporator temperature is brought up to 140 ℃.The results are shown in the table 4.Reach 12 cycles once more.Conversion ratio is reduced to 39.2% from 73.1%.Aldolize, aldehyde are hydrogenated to pure and mild olefin hydrogenation and become alkane inoperative equally here.
The experimental result of table 4: embodiment 2.4
Figure BYZ000003949305500291
Therefore embodiment shows the stabilization of the secondary sterically hindered amines of general formula I for catalyst system, shows the detrimental effect that stability does not take place for the aldolize of aldehyde simultaneously.

Claims (21)

1. carbonylation method, enable in the method in the presence of the metal complex catalysts of periodic table of elements group VIII metal, to be reacted by at least a compound of carbon monoxide carbonylation and carbon monoxide, this catalyst organic phosphorus compound is as part, it is characterized in that carbonylation is to carry out in the presence of the secondary sterically hindered amines with following general structural formula 1:
Figure FSB00000453263900011
Ra, Rb, Rc, Rd, Re and Rf are identical or different alkyl in the formula, and they are together connected to each other or do not link together.
2. according to the method for claim 1, it is characterized in that having 2,2,6, the amine of 6-tetramethyl piperidine unit II is used as secondary amine:
3. according to the method for claim 1 or 2, it is characterized in that at least a in the compound of IIg of structural formula II b as secondary amine:
Figure FSB00000453263900013
Figure FSB00000453263900021
N=1 to 20 in the formula
Figure FSB00000453263900022
N=1 to 12 in the formula
Figure FSB00000453263900023
N=1 to 17 in the formula
Figure FSB00000453263900024
4. according to the method for claim 1 or 2, it is characterized in that having at least a compound of formula III as the phosphorus organic ligand at least a compound of two or more functional groups of VI or formula III to VI:
PR 2R 3R 4 III
PR 2R 3(TR 5) IV
PR 2(TR 5)(TR 6) V
P(TR 5)(TR 6)(TR 7) VI
Wherein T=O, NH or NR 8, R 2To R 8Be to have the identical or different organic group of 1-50 carbon atom and be connected to each other or be not connected to each other via covalent bond.
5. according to the method for claim 4, it is characterized in that at least a compound of formula VIIc-9, VIIc-10 or VIIc-11 is used as the phosphorus organic ligand:
Wherein X and Y have the replacement of 1-50 carbon atom or unsubstituted aliphatic series, alicyclic, aliphatic-alicyclic, heterocycle family, aliphatic series-heterocycle family, aromatics-aromatics or aliphatic-aromatic alkyl, wherein X and Y are identical or different or with covalent keyed jointing each other, Q preferably has the replacement of divalence at least of 1 to 50 carbon atom or unsubstituted aliphatic series, alicyclic, aliphatic-alicyclic, heterocycle family, aliphatic series-heterocycle family, aromatics, aromatics-aromatics or an aliphatic-aromatic alkyl, and wherein substituted hydrocarbon radical has and is selected from-N (R 20) 2,-NHR 20,-NH 2, fluorine, chlorine, bromine, iodine ,-OH ,-CN ,-C (O)-R 20,-C (O) H or-C (O) O-R 20,-CF 3,-O-R 20,-C (O) N-R 20,-OC (O)-R 20And/or-Si (R 20) 3In substituting group as substituting group, R wherein 20Be the monovalence alkyl that preferably has 1-20 carbon atom, if there are a plurality of alkyl R 20, then these can be identical or different, and R wherein 16To R 19Be independently from each other respectively that monovalence replaces or unsubstituted aliphatic series, alicyclic, aromatics, heteroaromatic, mixed aliphatic series-alicyclic, mixed aliphatic series-aromatics, heterocycle family, mixed aliphatic series-heterocycle family hydrocarbyl group, H, F, Cl, Br, I with 1-50 carbon atom ,-CF 3,-CH 2(CF 2) jCF 3, j=0-9 wherein ,-OR 21,-COR 21,-CO 2R 21,-CO 2M ,-SR 21,-SO 2R 21,-SOR 21,-SO 3R 21,-SO 3M ,-SO 2NR 21R 22,-NR 21R 22,-N=CR 21R 22, R wherein 21And R 22The monovalence that be independently from each other H, has 1 to 25 carbon atom replaces or unsubstituted aliphatic series and aromatic hydrocarbyl, M be alkali metal ion, pro forma half alkaline-earth metal ions, ammonium ion or
Figure FSB00000453263900041
Ion, or adjacent radicals R 16To R 19Form together to condense and replace or unsubstituted aromatics, heteroaromatic, aliphatic series, mixing aromatic-aliphatic or mixing heteroaromatic-aliphatic member ring systems; Wherein substituted hydrocarbon radical has and is selected from-N (R 23) 2,-NHR 23,-NH 2, fluorine, chlorine, bromine, iodine ,-OH ,-CN ,-C (O)-R 23,-C (O) H or-C (O) O-R 23,-CF 3,-O-R 23,-C (O) N-R 23,-OC (O)-R 23And/or-Si (R 23) 3In substituting group as substituting group, when there being a plurality of alkyl R 23The time, these can be identical or different, and radicals R 16, R 17, R 18And R 19Be identical or different.
6. according to the method for claim 4, it is characterized in that the compound of formula VIIb-1 or VIIb-2 is as the phosphorus organic ligand
Figure FSB00000453263900042
K=2 in the formula, R 16, R 17, R 18And R 19Has the meaning that provides for formula VIIc-9 to VIIc-11, Q has the bivalent substituted of 1 to 50 carbon atom or unsubstituted aliphatic series, alicyclic, mixed aliphatic series-alicyclic, heterocycle family, mixed aliphatic series-heterocycle family, aromatics, heteroaromatic, mixed aliphatic series-aromatic hydrocarbon radical, wherein the aliphatic series part of Q can contain aerobic, sulphur and/or nitrogen, and wherein substituted hydrocarbon radical Q can have and be used for R 16To R 19Identical substituting group is as substituting group.
7. according to the method in claim 1 or 2, it is characterized in that the phosphorus organic ligand is 0.1/1 to 1/1000 use with the molar ratio of metal and part, the phosphorus organic ligand also is present in the reactant mixture as free ligand under this ratio.
8. according to the method for claim 1 or 2, it is characterized in that the alefinically unsaturated compounds that is selected from replacement or unsubstituted alpha-olefin, internal olefin, cycloolefin, alkenyl alkyl ethers and the alkenols is used as the initial compounds for the treatment of carbonylation.
9. according to the method for claim 1 or 2, it is characterized in that,, be selected from least a material in hydrogen, water, amine or the alcohol as other reactant except that carbon monoxide and treating the initial compounds of carbonylation.
10. according to the method for claim 1 or 2, it is characterized in that except that carbon monoxide and treating the initial compounds of carbonylation, hydrogen is as other reactant with carry out hydroformylation at least.
11. the method according to claim 1 or 2 is characterized in that, cobalt or rhodium are as the metal of periodic table group VIII.
12. the method according to claim I or 2 is characterized in that, secondary sterically hindered amines according to and catalyst metals between 0.1: 1 to 100: 1 molar ratio be used for reactant mixture.
13. a mixture, it comprises and contains the phosphorus organic compound as metal complex catalysts part, periodic table of elements group VIII metal and the secondary sterically hindered amines with following general structural formula I:
Ra, Rb, Rc, Rd, Re and Rf are identical or different alkyl in the formula, and they can be together connected to each other.
14. according to the mixture of claim 13, it is characterized in that containing and have 2,2,6, the amine of 6-tetramethyl piperidine unit II is as secondary amine:
Figure FSB00000453263900061
15. the mixture according to claim 13 or 14 is characterized in that, contains at least a compound in the compound that is selected from formula IIb to IIg as secondary amine:
N=1 to 20 in the formula
Figure FSB00000453263900063
N=1 to 12 in the formula
Figure FSB00000453263900071
N=to 17 in the formula
Figure FSB00000453263900072
16., it is characterized in that containing and comprise at least a compound of formula III in as the phosphorus organic ligand at least a compound of two or more functional groups of VI or formula III to VI according to the mixture of claim 13 or 14
PR 2R 3R 4 III
PR 2R 3(TR 5) IV
PR 2(TR 5)(TR 6) V
P(TR 5)(TR 6)(TR 7) VI
Wherein T=O, NH or NR 8, R 2To R 8Be to have the identical or different organic group of 1-50 carbon atom and be connected to each other or be not connected to each other via covalent bond.
17. according to the mixture of claim 13 or 14, at least a compound that it is characterized in that containing formula VIIc-9, VIIc-10 or VIIc-11 is as the phosphorus organic ligand:
Figure FSB00000453263900073
Figure FSB00000453263900081
Wherein X and Y have the replacement of 1-50 carbon atom or unsubstituted aliphatic series, alicyclic, aliphatic-alicyclic, heterocycle family, aliphatic series-heterocycle family, aromatics-aromatics or aliphatic-aromatic alkyl, wherein X and Y are identical or different or with covalent keyed jointing each other, Q preferably has the replacement of divalence at least of 1 to 50 carbon atom or unsubstituted aliphatic series, alicyclic, aliphatic-alicyclic, heterocycle family, aliphatic series-heterocycle family, aromatics, aromatics-aromatics or an aliphatic-aromatic alkyl, and wherein substituted hydrocarbon radical has and is selected from-N (R 20) 2,-NHR 20,-NH 2, fluorine, chlorine, bromine, iodine ,-OH ,-CN ,-C (O)-R 20,-C (O) H or-C (O) O-R 20,-CF 3,-O-R 20,-C (O) N-R 20,-OC (O)-R 20And/or-Si (R 20) 3In substituting group as substituting group, R wherein 20Be the monovalence alkyl that preferably has 1-20 carbon atom, if there are a plurality of alkyl R 20, then these can be identical or different, and R wherein 16To R 19Be independently from each other respectively that monovalence replaces or unsubstituted aliphatic series, alicyclic, aromatics, heteroaromatic, mixed aliphatic series-alicyclic, mixed aliphatic series-aromatics, heterocycle family, mixed aliphatic series-heterocycle family hydrocarbyl group, H, F, Cl, Br, I with 1-50 carbon atom ,-CF 3,-CH 2(CF 2) jCF 3, j=0-9 wherein ,-OR 21,-COR 21,-CO 2R 21,-CO 2M ,-SR 21,-SO 2R 21,-SOR 21,-SO 3R 21,-SO 3M ,-SO 2NR 21R 22,-NR 21R 22,-N=CR 21R 22, R wherein 21And R 22The monovalence that be independently from each other H, has 1 to 25 carbon atom replaces or unsubstituted aliphatic series and aromatic hydrocarbyl, and M is alkali metal ion, first alkaline-earth metal ions of form, ammonium ion or
Figure FSB00000453263900082
Ion, or adjacent radicals R 16To R 19Form together to condense and replace or unsubstituted aromatics, heteroaromatic, aliphatic series, mixing aromatic-aliphatic or mixing heteroaromatic-aliphatic member ring systems; Wherein substituted hydrocarbon radical has and is selected from-N (R 23) 2,-NHR 23,-NH 2, fluorine, chlorine, bromine, iodine ,-OH ,-CN ,-C (O)-R 23,-C (O) H or-C (O) O-R 23,-CF 3,-O-R 23,-C (O) N-R 23,-OC (O)-R 23And/or-Si (R 23) 3In substituting group as substituting group, when there being a plurality of alkyl R 23The time, these can be identical or different, and radicals R 16, R 17, R 18And R 19Be identical or different.
18. according to the mixture of claim 13 or 14, the compound that it is characterized in that comprising formula VIIb-1 or VIIb-2 is as the phosphorus organic ligand:
Figure FSB00000453263900091
K=2 in the formula, R 16, R 17, R 18And R 19Has the meaning that provides for formula VIIc-9 to VIIc-11, Q has the bivalent substituted of 1 to 50 carbon atom or unsubstituted aliphatic series, alicyclic, mixed aliphatic series-alicyclic, heterocycle family, mixed aliphatic series-heterocycle family, aromatics, heteroaromatic, mixed aliphatic series-aromatic hydrocarbon radical, wherein the aliphatic series part of Q can contain aerobic, sulphur and/or nitrogen, and wherein substituted hydrocarbon radical Q can have and be used for R 16To R 19Identical substituting group is as substituting group.
19. the mixture according to claim 13 or 14 is characterized in that, the phosphorus organic ligand according to and metal between 0.1: 1 to 100: 1 molar ratio exist.
20. the mixture according to claim 13 or 14 is characterized in that, cobalt or rhodium exist as the metal of periodic table group VIII.
21. the mixture according to claim 13 or 14 is characterized in that, secondary sterically hindered amines according to and catalyst metals between 0.1: 1 to 100: 1 molar ratio exist.
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